Fast prediction of adsorption properties for platinum nanocatalysts with generalized coordination numbers.

Platinum is a prominent catalyst for a multiplicity of reactions because of its high activity and stability. As Pt nanoparticles are normally used to maximize catalyst utilization and to minimize catalyst loading, it is important to rationalize and predict catalytic activity trends in nanoparticles in simple terms, while being able to compare these trends with those of extended surfaces. The trends in the adsorption energies of small oxygen- and hydrogen-containing adsorbates on Pt nanoparticles of various sizes and on extended surfaces were analyzed through DFT calculations by making use of the generalized coordination numbers of the surface sites. This simple and predictive descriptor links the geometric arrangement of a surface to its adsorption properties. It generates linear adsorption-energy trends, captures finite-size effects, and provides more accurate descriptions than d-band centers and usual coordination numbers. Unlike electronic-structure descriptors, which require knowledge of the densities of states, it is calculated manually. Finally, it was shown that an approximate equivalence exists between generalized coordination numbers and d-band centers.

[1]  C. Kittel.  Introduction to solid state physics , 1954 .

[2]  V. Heine,et al.  Multi-Atom Bonding in Aluminium over a Wide Range of Coordination Number , 1991 .

[3]  S. T. Buckland,et al.  An Introduction to the Bootstrap. , 1994 .

[4]  G. Kresse,et al.  Structural and electronic properties of rhodium surfaces: an ab initio approach , 1996 .

[5]  Kresse,et al.  Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. , 1996, Physical review. B, Condensed matter.

[6]  E. Shustorovich,et al.  The UBI-QEP method: A practical theoretical approach to understanding chemistry on transition metal surfaces , 1998 .

[7]  John P. Perdew,et al.  Molecular and solid‐state tests of density functional approximations: LSD, GGAs, and meta‐GGAs , 1999 .

[8]  J. G. Chen,et al.  Modification of the surface electronic and chemical properties of Pt(111) by subsurface 3d transition metals. , 2004, The Journal of chemical physics.

[9]  H. Gasteiger,et al.  Activity benchmarks and requirements for Pt, Pt-alloy, and non-Pt oxygen reduction catalysts for PEMFCs , 2005 .

[10]  N. Lewis,et al.  Powering the planet: Chemical challenges in solar energy utilization , 2006, Proceedings of the National Academy of Sciences.

[11]  A. Gross.  Adsorption at Nanostructured Surfaces from First Principles , 2008 .

[12]  Michael Eikerling,et al.  Ab Initio Study of Stability and Site-Specific Oxygen Adsorption Energies of Pt Nanoparticles , 2009 .

[13]  D. J. Mowbray,et al.  Trends in CO Oxidation Rates for Metal Nanoparticles and Close-Packed, Stepped, and Kinked Surfaces , 2009 .

[14]  A. Gross,et al.  Strain and coordination effects in the adsorption properties of early transition metals: A density-functional theory study , 2010 .

[15]  Nuria Garcia-Araez,et al.  Cathodic Corrosion: A Quick, Clean, and Versatile Method for the Synthesis of Metallic Nanoparticles** , 2011, Angewandte Chemie.

[16]  V. A. Morozov,et al.  Finite Size Effects in Chemical Bonding: From Small Clusters to Solids , 2011 .

[17]  J. Nørskov,et al.  Atomic-Scale Modeling of Particle Size Effects for the Oxygen Reduction Reaction on Pt , 2011 .

[18]  W. Goddard,et al.  Using Photoelectron Spectroscopy and Quantum Mechanics to Determine d-Band Energies of Metals for Catalytic Applications , 2012 .

[19]  Andrew J. Medford,et al.  Finite-Size Effects in O and CO Adsorption for the Late Transition Metals , 2012, Topics in Catalysis.

[20]  J. Rossmeisl,et al.  Physical and chemical nature of the scaling relations between adsorption energies of atoms on metal surfaces. , 2012, Physical review letters.

[21]  Ib Chorkendorff,et al.  The effect of size on the oxygen electroreduction activity of mass-selected platinum nanoparticles. , 2012, Angewandte Chemie.

[22]  V. Viswanathan,et al.  Theoretical analysis of the effect of particle size and support on the kinetics of oxygen reduction reaction on platinum nanoparticles. , 2012, Nanoscale.

[23]  M. El-Sayed,et al.  Enhancing colloidal metallic nanocatalysis: sharp edges and corners for solid nanoparticles and cage effect for hollow ones. , 2013, Accounts of chemical research.

[24]  W. Goddard,et al.  Finding Correlations of the Oxygen Reduction Reaction Activity of Transition Metal Catalysts with Parameters Obtained from Quantum Mechanics , 2013 .